CN111151295A - Surface modified composite carbon material for oxidative desulfurization and preparation method thereof - Google Patents
Surface modified composite carbon material for oxidative desulfurization and preparation method thereof Download PDFInfo
- Publication number
- CN111151295A CN111151295A CN201911425918.XA CN201911425918A CN111151295A CN 111151295 A CN111151295 A CN 111151295A CN 201911425918 A CN201911425918 A CN 201911425918A CN 111151295 A CN111151295 A CN 111151295A
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- China
- Prior art keywords
- carbon material
- surface modified
- modified composite
- composite carbon
- ionic liquid
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 117
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 36
- 230000023556 desulfurization Effects 0.000 title abstract description 36
- 150000001721 carbon Chemical class 0.000 claims abstract description 33
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 239000011831 acidic ionic liquid Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 239000000295 fuel oil Substances 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 150000003568 thioethers Chemical class 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910006069 SO3H Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 21
- 229910052717 sulfur Inorganic materials 0.000 description 21
- 239000011593 sulfur Substances 0.000 description 21
- 239000003921 oil Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 18
- 230000004048 modification Effects 0.000 description 13
- 238000012986 modification Methods 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000010992 reflux Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- -1 sulfone compounds Chemical class 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 5
- NFKMSYOEMWGTMW-UHFFFAOYSA-N 5-sulfanylidenedibenzothiophene Chemical compound C1=CC=C2S(=S)C3=CC=CC=C3C2=C1 NFKMSYOEMWGTMW-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000009489 vacuum treatment Methods 0.000 description 4
- MVVMXXNXJFRKON-UHFFFAOYSA-N 4,6-dimethyl-5-sulfanylidenedibenzothiophene Chemical compound C12=CC=CC(C)=C2S(=S)C2=C1C=CC=C2C MVVMXXNXJFRKON-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene sulfoxide Natural products C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- OJVIVHDZFOTDOZ-UHFFFAOYSA-N 1-sulfanylidene-1-benzothiophene Chemical compound S1(C=CC2=C1C=CC=C2)=S OJVIVHDZFOTDOZ-UHFFFAOYSA-N 0.000 description 1
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical compound S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 description 1
- AXLMWFQRHUVZLP-UHFFFAOYSA-N 2-(3-methylimidazol-3-ium-1-yl)propanoic acid chloride Chemical compound [Cl-].C(=O)(O)C(C)[N+]1=CN(C=C1)C AXLMWFQRHUVZLP-UHFFFAOYSA-N 0.000 description 1
- AQFPAMFDGCIZAY-UHFFFAOYSA-K C(CCC)N1CN(C=C1)C.[Al](Cl)(Cl)Cl Chemical compound C(CCC)N1CN(C=C1)C.[Al](Cl)(Cl)Cl AQFPAMFDGCIZAY-UHFFFAOYSA-K 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ULIJLHUMGZOVKE-UHFFFAOYSA-N S(O)(O)(=O)=O.CN1C=NC=C1.C(CC)S(=O)(=O)O Chemical compound S(O)(O)(=O)=O.CN1C=NC=C1.C(CC)S(=O)(=O)O ULIJLHUMGZOVKE-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001009 interstitial alloy Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- ZNCXUFVDFVBRDO-UHFFFAOYSA-N pyridine;sulfuric acid Chemical compound [H+].[O-]S([O-])(=O)=O.C1=CC=[NH+]C=C1 ZNCXUFVDFVBRDO-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/20—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of oil product processing, and discloses a surface modified composite carbon material for oxidative desulfurization and a preparation method thereof. The preparation method comprises the following steps: 1) carrying out oxidation treatment on the carbon material, and carrying out high-temperature annealing treatment in a protective atmosphere to obtain a modified carbon material; 2) the modified carbon material is taken as a carrier, the acidic ionic liquid is taken as an active component, and the active component is loaded on the carrier to obtain the surface modified composite carbon material. The method is simple, and the obtained surface modified composite carbon material has the characteristics that the physical action of the active components and the carrier is strong, and the distribution state of the active components on the surface is a quasi-liquid phase environment.
Description
Technical Field
The invention belongs to the technical field of oil product processing, and particularly relates to a surface modified composite carbon material for removing sulfides in fuel oil through oxidation and a preparation method thereof.
Background
Fuel oil contains a large amount of sulfides, which form SO after combustionx，SOxIs one of the main air pollution sources. Thus, many national regulations impose a requirement to reduce the sulphide content of fuel oils. The central economic job conference held in 12 months in 2019 clearly emphasizes: the three main attack and solidness warfare which includes 'pollution prevention and control' needs to be played, the key point is to play blue sky, green water and clean soil guard warfare, perfect a relevant governing mechanism and emphasize good source prevention and control. The fuel oil desulfurization is to control SO from the sourcexThe air pollution is reduced. Among the existing desulfurization measures, hydrodesulfurization, extractive desulfurization, adsorption desulfurization, biological desulfurization and oxidative desulfurization have the following defects: hydrodesulfurization needs high temperature and high pressure, has harsh conditions, consumes hydrogen sources, reduces octane number, and is more difficult to remove sulfides such as thiophene, benzothiophene and the like; the problems of low adsorption capacity, difficult regeneration, competitive adsorption and the like existing in adsorption desulfurization also need to be solved urgently; biological desulfurization is under study. Oxidative desulfurization is considered to be the most promising deep desulfurization technique for fuel oil. Under normal temperature and pressure, the oxidation desulfurization technology adopts a catalytic oxidation method to oxidize sulfides which are difficult to be removed by hydrodesulfurization into sulfone compounds with strong polarity, and then adopts methods such as polar solvent extraction, adsorbent adsorption, distillation or pyrolysis to remove the sulfone compounds in fuel oil. The research on the oxidative desulfurization of fuel oil originates from the middle part of the last century, and the early oxidative desulfurization technology mostly adopts organic acid or inorganic acid as a catalyst. In 1996, a petrostar company firstly develops an industrial deep desulfurization technology (CED technology), which belongs to an acetic acid/hydrogen peroxide system, can reduce sulfides in fuel oil from 4200ppm to below 10ppm after two-step process treatment of oxidation and extraction, and carries out industrial production in a scale of 5000 barrels per day. In 2001, Unipure company developed ASR-2 technology, which is also an organic liquid acid and hydrogen peroxide system and realizes industrial production. Although these techniques have excellent oxidative desulfurization performance, the catalyst cannot be recycled and corrodes equipment. Thus, isIn order to solve the problems, documents or patents successively disclose that the metal catalyst is used for oxidative desulfurization, but the preparation methods are complex, the service life is short, the selectivity is not ideal enough, and the cost is high. In order to solve the problems, the invention provides a preparation method of a carbon material surface modified composite material which is simple to prepare, free of metal, excellent in oxidation performance and good in durability, and an application of the carbon material surface modified composite material in oxidative desulfurization.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a surface modified composite carbon material for oxidative desulfurization and a preparation method thereof. The composite material has the advantages of high catalytic activity, high selectivity, good stability and the like.
The invention also aims to provide the application of the surface modified composite carbon material in the oxidative removal of sulfide in fuel oil.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a surface modified composite carbon material comprises the following steps:
1) carrying out oxidation treatment on the carbon material, and carrying out high-temperature annealing treatment in a protective atmosphere to obtain a modified carbon material;
2) the modified carbon material is taken as a carrier, the acidic ionic liquid is taken as an active component, and the active component is loaded on the carrier to obtain the surface modified composite carbon material.
The acidic ionic liquid is more than one of the following formulas I-V:
in the formula I, R1＝CH3(CH2)nN is an integer of 0 to 8;
R2＝CH2(CH2)nSO3h, n ═ 2, 3 or CH2(CH2)nCOOH，n＝0，1，2，3；
R3＝CH3；X-Is C1-，Br-，(H2PO4)-，(HSO4)-，TFSI(CF3-(O)S(O)-N-(O)S(O)-CF3)，(BF4)-，(PF6)-，CH3COO-；
In the formula I, R1And R2The groups (A) and (B) may be interchanged;
in the formula II R1＝CH3(CH2)nN is an integer of 0 to 8, or R1＝(CH2)nCOOH n＝1，2，3；
R2＝CH2(CH2)nSO3H n ═ 2, 3, or CH2(CH2)nCOOH n is 0, 1, 2, 3; in the formula II R1And R2The groups (A) and (B) may be interchanged;
r in the formulae III to V2Each is CH2(CH2)nSO3H, n ═ 2, 3 or CH2(CH2)nCOOH, n is 0, 1, 2, 3; or CH3(CH2)nN is an integer of 0 to 8;
n in the formulae IV to V1Independently an integer of 2-6.
The high-temperature annealing temperature is 600-1200 ℃, and the high-temperature annealing time is 2-6 hours. The heating rate of the high-temperature annealing is 3-10 ℃/min.
The carbon material in the step 1) includes, but is not limited to, any one of the following carbon materials: wood activated carbon, mineral raw material activated carbon, waste plastic or activated carbon made of rubber.
The protective atmosphere is an atmosphere provided by vacuum conditions or protective gas. The protective gas is nitrogen, helium, argon, etc.
The oxidation treatment is gas phase oxidation treatment or liquid phase oxidation treatment.
The gas-phase oxidation treatment is to carry out heat treatment for 2-7 hours at 200-500 ℃ in an air atmosphere or an oxygen atmosphere; the heating rate of the heat treatment is 2-10 ℃/min.
The liquid-phase oxidation treatment is oxidation treatment by adopting an oxidant. The oxidant is nitric acid, the mass concentration of the solution is 15-68%, potassium permanganate, hydrogen peroxide (the concentration is 30%), sulfuric acid, ammonium persulfate and the like, and the time of oxidation treatment is 2-36 h.
The specific steps of loading the active component on the carrier are as follows: mixing the acidic ionic liquid with water to obtain an acidic ionic liquid solution; and mixing the acidic ionic liquid solution with the modified carbon material, stirring, removing the solvent, and drying to obtain the surface modified composite carbon material.
The mass concentration of the acidic ionic liquid solution is 5-85%; the dosage of the acidic ionic liquid solution and the modified carbon material is 2-6mL of solution/g of modified carbon material or the equivalent volume impregnation method is satisfied; the stirring is high-speed stirring, ultrasonic dispersion is carried out before stirring, and the ultrasonic time is 20-40 min.
The stirring temperature is 20-70 ℃, and the stirring time is 12-30 hours.
The solvent removal is rotary evaporation solvent removal.
The surface modified composite carbon material is used for oxidizing and removing sulfide in fuel oil.
The application specifically comprises the steps of taking a surface modified composite carbon material as a catalyst and taking H2O2The fuel oil is taken as an oxidant, and sulfide in the fuel oil is removed in an oxidizing-extracting mode in an extracting agent and the fuel oil.
The extractant is more than one of acetonitrile, pyrrolidone, methanol, Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) or common ionic liquid (1-butyl-3-methylimidazole aluminum trichloride salt ([ BMIM)]Cl/AlCl3) 1-butyl-3-methylimidazolium hexafluorophosphate ([ BMIM)]PF6)、[BMIM][BF4]、[BMIM][OcSO4]、[MMIM][DMP]And [ BMIM ]][Cu2Cl2]Plasma liquid).
The surface modified composite carbon material takes a modified carbon material as a carrier and acidic ionic liquid as an active component, and strong pi-pi action, van der Waals force, electrostatic force, polarization and the like are formed between the carrier and the active component through pi electrons on the surface of the carbon material and pi electrons on a cation imidazole ring of the ionic liquid, so that the active component is firmly adsorbed on the surface of the carrier.
The surface modified composite carbon material has the advantages and beneficial effects that:
(1) the method comprises the steps of firstly carrying out oxidation treatment on the surface of the carbon material to increase the number of polar groups on the surface of the carbon material, then carrying out high-temperature annealing treatment under a protective atmosphere to remove the surface groups and leave surface defects, thus obtaining the modified carbon material surface, wherein the modified carbon material surface has strong interaction on the acidic ionic liquid serving as an active component on one hand, so that the ionic liquid can be firmly fixed on a carrier, the service life of the composite material is prolonged, and on the other hand, the defective carbon material surface and the active component cooperate to improve the catalytic oxidation efficiency.
(2) The composite material is simple to prepare, is green, is a metal-free composite material, and has an oxidation desulfurization effect comparable to that of a traditional metal catalyst.
(3) The invention forms a pseudo-liquid phase reaction site: the acidic ionic liquid as the active component has two distribution forms on the surface of the carrier, one is simply adsorbed on the surface, and the other is in the form of oriented and ordered arrangement in a quasi-liquid state and firmly anchored on the surface of the carrier, and the distribution forms a quasi-liquid phase catalytic environment different from the traditional liquid-solid and gas-solid catalysis for catalytic reaction, so that the environment has better characteristics of mass and heat transfer, and further improves the reaction activity and the catalytic efficiency.
(4) The composite material has excellent performance, and has excellent oxidation desulfurization effect under extremely low sulfide concentration, such as: the content of sulfide (DBT) is 50ppm, and the desulfurization degree can reach more than 98%.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The loading amount of the active components in the composite carbon material is 4-55 wt%.
Example 1
A preparation method of a surface modified composite carbon material comprises the following steps:
(1) preparing an oxidized surface modified carbon material: placing a proper amount of active carbon with a brand number of CPL (Shanghai Hui chemical Co., Ltd.) or AC-Y (Achan Jian river active carbon Co., Ltd.) in a crucible, placing the crucible in a high-temperature furnace for gas phase oxidation treatment at 400 ℃ for 6h, and setting the programmed heating rate to be 5 ℃/min to obtain oxidized surface modified carbon materials CPL400 and AC-Y400;
(2) carbon material surface modification material: placing the oxidized surface modified carbon material prepared in the step (1) in a high-temperature furnace under the nitrogen atmosphere for annealing at 1000 ℃ for 4h, and setting the programmed heating rate at 10 ℃/min to obtain carbon material surface modified materials CPL-4-1000 and AC-Y-4-1000;
(3) preparing a surface modified composite carbon material: taking 1-propylsulfonic acid-3-methylimidazole bisulfate PrSO3HMIm[HSO4]1.2g of acidic ionic liquid is dissolved in 5mL of deionized water to form PrSO3HMIm[HSO4]Adding 2.0g of CPL-4-1000 or AC-Y-4-1000 carbon material surface modification material obtained in the step (2) into the solution under high-speed stirring at room temperature, performing ultrasonic treatment for 30min, then stirring at room temperature for 24h at high speed, spin-drying the solvent, and performing vacuum treatment at 105 ℃ for 24h to obtain the surface modified composite carbon material A (CPL-4-1000/PrSO)3HMIm[HSO4])。
PrSO3HMIm[HSO4]：
Considering that thiophene compounds in fuel oil, especially thiophene compounds with aromatic hydrocarbon groups are difficult to remove, the normal octane solution containing dibenzothiophene sulfide is used as simulated fuel oil, wherein the sulfur content is 50 ppm. Taking 10mL of the simulated fuel oil, and then sequentially adding a surface modified composite carbon material A (CPL-4-1000/PrSO)3HMIm[HSO4])50mg, 2-15mL acetonitrile can be added as extractant oil volume ratio extractant/simulated oil V/V (0.2-1.5), also in the following examples, 30% hydrogen peroxide solution is added as oxygen-sulfur molar ratio O/S (15-50) (wherein oxygen-sulfur ratio is about 25, preferably 28uL, also in the following examples) 30 uL; refluxing under magnetic stirring in oil bath at constant temperature of 60 deg.C (constant temperature oil bath temperature of 30-80 deg.C, preferably 60 deg.C) for 2.5h, and measuring upper oil phaseSulfur content and desulfurizing rate up to 99%.
Example 2
A preparation method of a surface modified composite carbon material comprises the following steps:
(1) preparing an oxidized surface modified carbon material: placing a proper amount of CPL active carbon (Shanghai Hui chemical Co., Ltd.) in a crucible, performing gas phase oxidation treatment for 6h at 350 ℃ in a high-temperature furnace, and setting the programmed heating rate to be 5 ℃/min to obtain an oxidized surface modified carbon material CPL 350;
(2) carbon material surface modification material: placing the oxidized surface modified carbon material prepared in the step (1) in a high-temperature furnace under the nitrogen atmosphere for annealing at 1000 ℃ for 4h, and setting the programmed heating rate at 10 ℃/min to obtain a carbon material surface modified material CPL-3-1000;
(3) preparing a surface modified composite carbon material: taking 1-propylsulfonic acid-3-methylimidazole chlorine salt PrSO31.2g of HMImCl acidic ionic liquid was dissolved in 5mL of deionized water to form uniform PrSO3Adding 2.0g of CPL-3-1000 carbon material surface modification material obtained in the step (2) into HMImCl solution while stirring at room temperature and high speed, performing ultrasonic treatment for 30min, then stirring at room temperature and high speed for 24h, spin-drying the solvent, and performing vacuum drying at 105 ℃ for 24h to obtain the surface modified composite carbon material B (CPL-3-1000/PrSO)3HMImCl)。
PrSO3HMIm[C1]：
Dibenzothiophene-containing fuel oil is dissolved in n-octane to serve as simulated fuel oil, wherein the sulfur content is 50 ppm: taking 10mL of the simulated fuel oil, and then sequentially adding the carbon material surface modified composite material B (CPL-3-1000/PrSO)3HMImCl)50mg, 2mL of extractant acetonitrile and 28 muL of 30% hydrogen peroxide solution; the mixture is stirred and refluxed for 2.5h under a constant temperature oil bath at 60 ℃, the upper layer of simulated gasoline is taken to measure the sulfur content, and the desulfurization rate reaches 98 percent.
Adopting n-octane solution containing benzothiophene sulfide as simulated fuel oil, wherein the sulfur content is 50ppm, and then sequentially adding 50mg of carbon material surface modified composite material B, 5mL of extracting agent acetonitrile and 28 mu L of 30% hydrogen peroxide solution; stirring and refluxing for 2.5h under a constant temperature oil bath at 60 ℃, and taking upper-layer simulated oil to measure the sulfur content and the desulfurization rate to reach 97%.
Example 3
A preparation method of a surface modified composite carbon material comprises the following steps:
(1) preparing an oxidized surface modified carbon material: placing a proper amount of ENOP active carbon (Shanghai Hui Pinghui chemical Co., Ltd.) with the brand number of ENOP in a crucible, placing the crucible in a high-temperature furnace for gas phase oxidation treatment at 400 ℃ for 6h, and setting the programmed heating rate to be 5 ℃/min to obtain an oxidized surface modified carbon material ENOP 400;
(2) carbon material surface modification material: placing the oxidized surface modified carbon material prepared in the step (1) in a high-temperature furnace in a nitrogen atmosphere for annealing at 1000 ℃ for 4h, and setting a programmed heating rate of 10 ℃/min to obtain a carbon material surface modified material ENOP-4-1000;
(3) preparing a surface modified composite carbon material: taking 1-butyl sulfonic acid-3-methylimidazole chlorine salt BSO31.2g of HMImCl acidic ionic liquid was dissolved in 5mL of deionized water to form uniform BSO3Adding 2.0g of ENOP-4-1000 carbon material surface modification material obtained in the step (2) into HMImCl solution while stirring at room temperature and high speed, performing ultrasonic treatment for 30min, then stirring at room temperature and high speed for 24h, spin-drying the solvent, and performing vacuum drying at 105 ℃ for 24h to obtain the surface modified composite carbon material C (ENOP-4-1000/BSO)3HMImCl)。
BSO3HMImCl：
Adopting normal octane solution containing dibenzothiophene sulfide as simulated fuel oil, wherein the sulfur content is 50 ppm: taking 10mL of the simulated fuel oil, and then sequentially adding carbon material surface modified composite material C (ENOP-4-1000/BSO)3HMImCl)50mg, an extractant acetonitrile 5mL, and a 30% hydrogen peroxide solution 28 μ L; the mixture is stirred and refluxed for 2.5h under a constant temperature oil bath at 60 ℃, the upper layer of simulated oil is taken to measure the sulfur content, and the desulfurization rate reaches 98 percent.
Adopting n-octane solution containing thiophene sulfide as simulated fuel oil, wherein the sulfur content is 50ppm, and then sequentially adding 50mg of surface modified composite carbon material C, 10mL of extracting agent acetonitrile and 28 mu L of 30% hydrogen peroxide solution; stirring and refluxing for 2.5h under a constant temperature oil bath at 60 ℃, and taking upper-layer simulated oil to measure the sulfur content and the desulfurization rate to reach 85 percent.
Example 4
(1) Preparing an oxidized surface modified carbon material: soaking a proper amount of CPL active carbon with a brand number of CPL in nitric acid with a concentration of 68% for 36h to obtain an oxidized surface modified carbon material CPL-N;
(2) carbon material surface modification material: placing the oxidized surface modified carbon material prepared in the step (1) in a high-temperature furnace under the nitrogen atmosphere, annealing for 4h at 900 ℃, and setting the programmed heating rate to be 10 ℃/min to obtain a carbon material surface modified material CPL-N-900;
(3) preparing a surface modified composite carbon material: dissolving 0.8g of 1-carboxyethyl-3-methylimidazolium chloride HOOCEMImCl acidic ionic liquid in 4mL of deionized water to form a HOOCEMImCl solution, adding 2.1g of the CPL-N-900 carbon material surface modification material obtained in the step (2) into the solution under high-speed stirring at room temperature, performing ultrasonic treatment for 30min, then stirring at room temperature for 24h at high speed, spin-drying the solvent, and performing vacuum treatment at 105 ℃ for 24h to obtain the surface-modified composite carbon material D (CPL-N-900/HOOCEMImCl).
The method adopts an n-octane solution containing 4, 6-dimethyl-dibenzothiophene sulfide as simulated fuel oil, wherein the sulfur content is 50 ppm: taking 10mL of the simulated fuel oil, and then sequentially adding 10mL of the surface modified composite carbon material D50mg, 10mL of the extracting agent acetonitrile and 28 muL of 30% hydrogen peroxide solution; and (3) refluxing for 3h under the constant-temperature oil bath at 60 ℃ by magnetic stirring, and taking the upper-layer simulated gasoline to measure the sulfur content, wherein the desulfurization rate reaches 98%.
HOOCEMImCl：
Adopting normal octane solution containing dibenzothiophene sulfide as simulated fuel oil, wherein the sulfur content is 50 ppm: taking 10mL of the simulated fuel oil, and then sequentially adding 50mg of the surface modified composite carbon material D, 5mL of the extracting agent acetonitrile and 28 mu L of 30% hydrogen peroxide solution; and (3) refluxing for 2h under the constant-temperature oil bath at 60 ℃ by magnetic stirring, and measuring the sulfur content by taking the upper-layer simulated gasoline, wherein the desulfurization rate reaches 98%.
Example 5
(1) Preparing an oxidized surface modified carbon material: soaking a proper amount of CPL active carbon with a brand number of CPL in nitric acid with a concentration of 68% for 36h to obtain an oxidized surface modified carbon material CPL-N;
(2) carbon material surface modification material: placing the oxidized surface modified carbon material prepared in the step (1) in a high-temperature furnace under the nitrogen atmosphere, annealing for 4h at 900 ℃, and setting the programmed heating rate to be 10 ℃/min to obtain a carbon material surface modified material CPL-N-900;
(3) preparing a surface modified composite carbon material: taking 1, 3-dicarboxymethylimidazole nitrate (BCINO)3) 0.8g of acidic ionic liquid was dissolved in 4mL of deionized water to form (BCINO)3) Adding 2.1g of CPL-N-900 carbon material surface modification material obtained in the step (2) into the solution while stirring at high speed at room temperature, performing ultrasonic treatment for 30min, then stirring at high speed for 24h at room temperature, spin-drying the solvent, and performing vacuum treatment for 24h at 105 ℃ to obtain the surface modified composite carbon material E (CPL-N-900/BCINO)3)。
BCINO3：
The method adopts an n-octane solution containing 4, 6-dimethyl-dibenzothiophene sulfide as simulated fuel oil, wherein the sulfur content is 50 ppm: taking 10mL of the simulated fuel oil, and then sequentially adding a surface modified composite carbon material E50mg, 10mL of an extracting agent acetonitrile and 28 muL of 30% hydrogen peroxide solution; and (3) refluxing for 3h under the constant-temperature oil bath at 60 ℃ by magnetic stirring, and taking the upper-layer simulated gasoline to measure the sulfur content, wherein the desulfurization rate reaches 96%.
Adopting normal octane solution containing dibenzothiophene sulfide as simulated fuel oil, wherein the sulfur content is 50 ppm: taking 10mL of the simulated fuel oil, and then sequentially adding 50mg of the surface modified composite carbon material E, 5mL of the extracting agent acetonitrile and 28 mu L of 30% hydrogen peroxide solution; and (3) refluxing for 2h under the constant-temperature oil bath at 60 ℃ by magnetic stirring, and taking the upper-layer simulated gasoline to measure the sulfur content, wherein the desulfurization rate reaches 94.5%.
Example 6
(1) Preparing an oxidized surface modified carbon material: soaking a proper amount of CPL active carbon with a brand number of CPL in nitric acid with a concentration of 68% for 36h to obtain an oxidized surface modified carbon material CPL-N;
(2) carbon material surface modification material: placing the oxidized surface modified carbon material prepared in the step (1) in a high-temperature furnace under the nitrogen atmosphere, annealing for 4h at 900 ℃, and setting the programmed heating rate to be 10 ℃/min to obtain a carbon material surface modified material CPL-N-900;
(3) preparing a surface modified composite carbon material: taking N-propylsulfonic acid pyridine bisulfate [ PSPy][HSO4]Dissolving 0.8g of acidic ionic liquid in 4mL of deionized water to form a solution, adding 2.1g of the CPL-N-900 carbon material surface modification material obtained in the step (2) into the solution under high-speed stirring at room temperature, performing ultrasonic treatment for 30min, then stirring the solution at room temperature for 24h at high speed, spin-drying the solvent, and performing vacuum treatment at 105 ℃ for 24h to obtain the surface-modified composite carbon material F (CPL-N-900/[ PSPy][HSO4])。
[PSPy][HSO4]：
The method adopts an n-octane solution containing 4, 6-dimethyl-dibenzothiophene sulfide as simulated fuel oil, wherein the sulfur content is 50 ppm: taking 10mL of the simulated fuel oil, and then sequentially adding a surface modified composite carbon material F50mg, 10mL of an extracting agent acetonitrile and 28 muL of 30% hydrogen peroxide solution; and (3) refluxing for 3h under the constant-temperature oil bath at 60 ℃ by magnetic stirring, and taking the upper-layer simulated gasoline to measure the sulfur content, wherein the desulfurization rate reaches 97%.
Adopting normal octane solution containing dibenzothiophene sulfide as simulated fuel oil, wherein the sulfur content is 50 ppm: taking 10mL of the simulated fuel oil, and then sequentially adding 50mg of the surface modified composite carbon material F, 5mL of the extracting agent acetonitrile and 28 mu L of 30% hydrogen peroxide solution; and (3) refluxing for 2h under the constant-temperature oil bath at 60 ℃ by magnetic stirring, and taking the upper-layer simulated gasoline to measure the sulfur content, wherein the desulfurization rate reaches 95%.
Comparative example 1
In the patent of application No. 200810123825.7, named as the application of molybdenum-based metal nitrogen carbide interstitial alloy in fuel oil desulfurization, the best desulfurization effect can be achieved, and only about 15mg/L of sulfide can be achieved, while the invention can remove over 95% of 50ppm sulfide, namely 50mg/L sulfide, and can reduce the content to 10 mg/L. Therefore, the invention can achieve better effect by adopting the non-metal catalyst.
The above embodiments are examples of the present invention, and it should be noted that the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent substitutions and are included in the scope of the present invention.
Claims (10)
1. A preparation method of a surface modified composite carbon material is characterized by comprising the following steps: the method comprises the following steps:
1) carrying out oxidation treatment on the carbon material, and carrying out high-temperature annealing treatment in a protective atmosphere to obtain a modified carbon material;
2) the modified carbon material is taken as a carrier, the acidic ionic liquid is taken as an active component, and the active component is loaded on the carrier to obtain the surface modified composite carbon material.
2. The method for preparing the surface modified composite carbon material according to claim 1, wherein the method comprises the following steps: the acidic ionic liquid is more than one of the following formulas I-V:
in the formula I, R1＝CH3(CH2)nN is an integer of 0 to 8;
R2＝CH2(CH2)nSO3h, n ═ 2, 3 or CH2(CH2)nCOOH，n＝0，1，2，3；
R3＝CH3；X-Is Cl-，Br-，(H2PO4)-，(HSO4)-，TFSI，(BF4)-，(PF6)-Or CH3COO-；
In the formula I, R1And R2The groups (A) and (B) may be interchanged;
in the formula II R1＝CH3(CH2)nN is an integer of 0 to 8, or R1＝(CH2)nCOOH n＝1，2，3；
R2＝CH2(CH2)nSO3H n ═ 2, 3, or CH2(CH2)nCOOH n is 0, 1, 2, 3; in the formula II R1And R2The groups (A) and (B) may be interchanged;
r in the formulae III to V2Each is CH2(CH2)nSO3H, n ═ 2, 3 or CH2(CH2)nCOOH, n is 0, 1, 2, 3; or CH3(CH2)nN is an integer of 0 to 8;
n in the formulae IV to V1Independently an integer of 2-6.
3. The method for preparing the surface modified composite carbon material according to claim 1, wherein the method comprises the following steps: the temperature of the high-temperature annealing is 600-1200 ℃, and the time of the high-temperature annealing is 2-6 hours;
the oxidation treatment is gas phase oxidation treatment or liquid phase oxidation treatment.
4. The method for preparing the surface modified composite carbon material according to claim 3, wherein the method comprises the following steps: the gas-phase oxidation treatment is to carry out heat treatment for 2-7h at 200-500 ℃ in an air atmosphere or an oxygen atmosphere;
the liquid-phase oxidation treatment is oxidation treatment by adopting an oxidant; the oxidant is nitric acid, potassium permanganate or hydrogen peroxide.
5. The method for preparing the surface modified composite carbon material according to claim 1, wherein the method comprises the following steps: the specific steps of loading the active component on the carrier are as follows: mixing the acidic ionic liquid with water to obtain an acidic ionic liquid solution; and mixing the acidic ionic liquid solution with the modified carbon material, stirring, removing the solvent, and drying to obtain the surface modified composite carbon material.
6. The method for preparing the surface modified composite carbon material according to claim 5, wherein the method comprises the following steps: the mass concentration of the acidic ionic liquid solution is 5-85%; the dosage of the acidic ionic liquid solution and the modified carbon material is 2-6mL of solution/g of modified carbon material or equal-volume impregnation is met;
carrying out ultrasonic dispersion before stirring, wherein the ultrasonic time is 20-40 min;
the stirring temperature is 20-70 ℃, and the stirring time is 12-30 hours.
7. The method for preparing the surface modified composite carbon material according to claim 1, wherein the method comprises the following steps:
the heating rate of the high-temperature annealing is 3-10 ℃/min;
the protective atmosphere is an atmosphere provided by vacuum conditions or protective gas.
8. A surface modified composite carbon material obtained by the preparation method of any one of claims 1 to 7.
9. The use of the surface modified composite carbon material of claim 1, wherein: the surface modified composite carbon material is used for oxidizing and removing sulfides in fuel oil.
10. Use according to claim 9, characterized in that: the application takes a surface modified composite carbon material as a catalyst and takes H2O2The fuel oil is taken as an oxidant, and sulfide in the fuel oil is removed in an oxidizing-extracting mode in an extracting agent and the fuel oil.
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